KR20110030695A - Hfo-1234ze mixed isomers with hfc-245fa as a blowing agent, aerosol, and solvent - Google Patents

Abstract

About 75-90% by weight of trans-1,3,3,3-tetrafluoropropene, about 1-15% by weight of cis-1,3,3,3-tetrafluoropropene and 1,1,3, A blowing agent composition comprising about 1-15% by weight of 3,3-pentafluoropropane is disclosed.

Description

HFO-1234ZEE mixed isomer having HFC-245FA as blowing agent, aerosol and solvent TECHNICAL FIELD [HFO-1234ZE MIXED ISOMERS WITH HFC-245FA AS A BLOWING AGENT]

This application claims priority to US Provisional Patent Application Serial No. 61 / 081,089, filed July 16, 2008 and US Provisional Patent Application Serial No. 61 / 081,597, filed August 18, 2008.

The present invention relates to compositions useful as blowing agents. More specifically, the present invention provides trans-1,3,3,3-tetrafluoropropene (trans-HFO-1234ze), cis-1,3,3,3-tetrafluoropropene (cis-HFO- 1234ze), and 1,1,1,3,3-pentafluoropropane (HFC-245fa), and the use of such a composition as a foam for forming a foam.

Typically, chlorofluorocarbons (CFCs) have been used as blowing agents. Recently, there is widespread concern that certain chlorofluorocarbons can be harmful to the global ozone layer. As a result, efforts to use halocarbons containing less or no chlorine substituents are widespread. Therefore, the production of hydrofluorocarbons or compounds containing only carbon, hydrogen and fluorine is of increasing interest to provide environmentally desirable products for use as blowing agents. It is also beneficial if these products have a relatively short atmospheric life such that the contribution to global warming is minimized. In this regard, trans-1,3,3,3-tetrafluoropropene (trans-1234ze) is a compound having the potential to be used as a zero ozone depletion index (ODP) and a low global warming index (GWP).

It is known in the art to produce HFO-1234ze (ie hydrofluoroolefin-1234ze). For example, US Pat. No. 5,710,352 teaches fluorination of 1,1,1,3,3-pentachloropropane (HCC-240fa) to form HCFC-1233zd and a small amount of HFO-1234ze. U.S. Patent 5,895,825 describes fluorination of HCFC-1233zd to form HFC-1234ze. U.S. Patent 6,472,573 also describes fluorination of HCFC-1233zd to form HFO-1234ze. US Pat. No. 6,124,510 describes the formation of cis and trans isomers of HFO-1234ze by dehydrofluorination of HFC-245fa. U.S. Patent 5,574,192 describes the formation of HFC-245fa via fluorination of HCC-240fa. U.S. Patent Application US20080051611 discloses primary dehydrofluorination of 1,1,1,3,3-pentafluoropropane, thus leading to cis-1,3,3,3-tetrafluoropropene, trans-1,3, A process for preparing trans-1,3,3,3-tetrafluoropropene is described that produces a mixture of 3,3-tetrafluoropropene and hydrogen fluoride. Hydrogen fluoride is then optionally recovered, followed by trans-1,3,3,3-tetrafluoropropene.

The reactor output of the dehydrofluorination reaction of 1,1,1,3,3-pentafluoropropane is trans-1,3,3,3-tetrafluoropropene (trans-HFO- 1234ze), cis-1,3,3,3-tetrafluoropropene (cis-HFO-1234ze), and 1,1,1,3,3-pentafluoropropane (HFC-245fa) It has now been found to generate. HF may also be present. The HF must be removed by any means known in the art before using such compositions as blowing agents. The composition meets the continuing requirements for replacement of CFCs and HCFCs. The composition has a zero ozone depletion index (ODP) and reduces the global warming index (GWP) while providing enhanced performance in blowing agent application. This reactor output composition is particularly attractive for use as a blowing agent in the application of foamed thermoset plastics, in particular polyurethane and polyisocyanurate insulation foams. The insulating properties of such compositions show an improvement in process properties through improved solubility and reduced vapor pressure, thereby reducing foam formation and cell formation and improving morphology. Further implementations relate to the use of reactor output compositions in pressurized one component foams. The essentially low vapor pressure of the blowing agent system as described by Raoult's law provides for the use of other higher pressures and / or higher molecular weight propellants, and also the required gas volume required for proper expansion without exceeding the pressure capacity of the package. Conforms to Such reactor output compositions are attractive for use as foaming agents in foamed thermoplastics such as polystyrene, polyethylene, polypropylene, polyethylene terephthalate and the like. This composition improves plasticizer upon melting of the polymer during blowing agent solubility and extrusion, thereby reducing the pressure in the barrel and in the die. In addition, the cell size is improved to form a low density foam.

Chlorofluorocarbons (CFCs) have been used as blowing agents, and in recent years there is widespread concern that certain chlorofluorocarbons may be harmful to the earth's ozone layer. Therefore, there is a need for replacement of CFCs used as blowing agents.

The present invention provides about 75-90% by weight of trans-1,3,3,3-tetrafluoropropene, about 1-25% by weight of cis-1,3,3,3-tetrafluoropropene and 1,1 A blowing agent comprising about 1-15% by weight of 3,3,3-pentafluoropropane.

The present invention is also directed to i) about 50-95% by weight of the blowing agent; And ii) hydrofluorocarbons, C ₁ -C ₆ hydrocarbons, C ₁ -C ₈ alcohols, ethers, diethers, aldehydes, ketones, hydrofluoroethers, C ₁ -C ₄ chlorocarbons, methyl formate, water And about 5-50% by weight of an auxiliary blowing agent comprising at least one component of carbon dioxide, C ₃ -C ₄ hydrofluoroolefin, and C ₃ -C ₄ hydrochlorofluoroolefin.

The present invention also provides a foaming composition comprising the blowing agent and optionally the auxiliary blowing agent and a mixture of foam forming components or components capable of forming a foam structure.

The invention also

a) about 75-90 wt% of trans-1,3,3,3-tetrafluoropropene, about 1-25 wt% of cis-1,3,3,3-tetrafluoropropene, and 1,1 Blowing agent comprising about 1-15% by weight of 3,3,3-pentafluoropropane; And

b) a foam forming component or a mixture of components capable of forming a foam structure

It provides a foam forming method comprising mixing.

The process can also be carried out optionally including auxiliary blowing agents.

In the method of dehydrofluorination of 1,1,1,3,3-pentafluoropropane, the reaction is not only an isomer of 1,3,3,3-tetrafluoropropene (both cis and trans) but also organic The component includes unreacted 1,1,1,3,3-pentafluoropropane. Depending on the dehydrofluorination technique used, some hydrogen fluoride may be produced. Hydrogen fluoride contamination is detrimental to the use of organic components and is therefore removed through any route known in the art, including scrubbing, distillation or extraction. The reactor output composition is controlled by operating conditions, i.e. residence time in the reactor, reactor temperature, catalyst used, reactor pressure, recycle stream composition as well as reactor design and configuration. The reactor output can be partially purified to remove other unwanted impurities that are also present due to the process or process conditions in addition to the hydrogen fluorides mentioned above. Reactor form may include, but is not limited to, residence time, multiple reactor stages, or multiple passes of reactants.

Catalytic dehydrofluorination of HFC-245fa includes cis-1,3,3,3-tetrafluoropropene, trans-1,3,3,3-tetrafluoropropene, residual HFC-245fa and possibly hydrogen Produces a result comprising fluoride. Dehydrofluorination reactions are well known in the art. Preferably dehydrofluorination of HFC-245fa is carried out in a fixed bed reactor in the gas phase, more preferably in the gas phase. The dehydrofluorination reaction can be carried out in any suitable reaction vessel or reactor, but it is preferably a material resistant to the corrosiveness of the hydrogen fluoride, such as nickel and its alloys including Hastelloy, Inconel, Incoloy and Monel. It may consist of a container made of or lined with a fluoropolymer. It may be a single or multiple reactor packed with a dehydrofluorination catalyst which may be in bulk form or supported metal fluoride oxide, bulk form or supported metal halide and carbon support transition metal, metal oxide and halide. Suitable catalysts include, but are not limited to, fluorinated chromia (fluorinated Cr ₂ O ₃ ), fluorinated alumina (fluorinated Al ₂ O ₃ ), metal fluorides (eg CrF ₃ , AlF ₃ ) and Carbon-supported transition metals (zero oxidation states) such as Fe / C, Co / C, Ni / C, Pd / C or transition metal halides. HFC-245fa is introduced into the reactor with any inert gas diluent such as nitrogen, argon and the like. In a preferred embodiment of the present invention, HFC-245fa is previously vaporized or preheated prior to entering the reactor. Alternatively, HFC-245fa is vaporized inside the reactor. Useful reaction temperatures may range from about 100-600 ° C. Preferred temperatures can range from about 150-450 ° C., and more preferred temperatures from about 200-350 ° C. The reaction can be carried out at atmospheric pressure, under-atmospheric pressure or under vacuum. The vacuum pressure may be about 5-760 torr. The contact time of HFC-245fa with the catalyst may range from about 0.5-120 seconds, preferably about 2-60 seconds, and most preferably about 5-40 seconds, although longer or shorter times may be used.

In a preferred embodiment, the reaction process flow is vertically downward or vertically upward through the catalyst bed in the reactor tube. It may also be advantageous to periodically regenerate the catalyst after long term use in situ in the reactor. Regeneration of the catalyst is known in the art, for example, by passing air or air diluted with nitrogen over the catalyst for about 0.5 hours to 3 days at a temperature of about 100-400 ° C., preferably about 200-375 ° C. It can be accomplished by any known means. It is HF treated at a temperature of about 25-400 ° C., preferably about 200-350 ° C. for metal fluoride metal oxides and metal fluoride catalysts, or about 100-400 ° C., preferably about 200 for carbon supported transition metal catalysts. H ₂ treatment at a temperature of −350 ° C. is followed. In this embodiment, dehydrofluorination produces some hydrogen fluoride, which is then removed. One mole of HF is produced for each mole of cis or trans-1,3,3,3-tetrafluoropropene.

In an alternative embodiment of the invention, the dehydrofluorination of HFC-245fa is also carried out at elevated temperatures, including but not limited to a strong caustic solution comprising KOH, NaOH, Ca (OH) ₂ and CaO with HFC-245fa. It can be carried out by reacting. In this case, the amount of caustic in the caustic solution is about 2-99% by weight, more preferably about 5-90% by weight, and most preferably about 10-80% by weight.

The reaction can be carried out at a temperature of about 20-100 ° C., more preferably about 30-90 ° C., and most preferably about 40-80 ° C. As mentioned above, the reaction can be carried out at atmospheric pressure, over-atmospheric pressure or under vacuum. The vacuum pressure may be about 5-760 torr. In addition, a solvent may optionally be used to assist in dissolving the organic compound in the caustic solution. This optional step can be carried out using solvents well known in the art for this purpose. Examples include polar solvents such as dioxamine, N-methyl pyrrolidone and the like. If dehydrofluorination is carried out using caustic techniques, an unmeasurable trace of hydrogen fluoride is produced. Phase transfer catalysts such as crown ethers or tetraalkyl ammonium salts can be used as needed.

In embodiments in which there is a hydrogen fluoride being recovered from the result of the dihydrofluoride reaction, the recovery of the hydrogen fluoride is preferably accomplished by passing the hydrogen fluoride by passing the composition resulting from the dehydrofluorination reaction through a sulfuric acid extractor. It is carried out by removing and subsequently desorbing the hydrogen fluoride extracted from sulfuric acid and then distilling the desorbed hydrogen fluoride. Separation can be carried out by adding sulfuric acid to the mixture in liquid or gaseous state. Typical weight ratios of sulfuric acid to hydrogen fluoride range from about 0.1: 1 to 100: 1. Starting with a liquid mixture of fluorocarbons and hydrogen fluoride, sulfuric acid is added to the mixture.

The amount of sulfuric acid required for the separation depends on the amount of HF present in the system. From the HF solubility in 100% sulfuric acid as a function of the temperature curve, a minimum substantial amount of sulfuric acid can be detected. For example, at 30 ° C., about 34 g of HF will be dissolved in 100 g of 100% sulfuric acid. However, at 100 ° C. only about 10 g of HF will be dissolved in 100% sulfuric acid. Preferably the sulfuric acid used in the present invention has a purity of about 50-100%.

In a preferred embodiment, the weight ratio of sulfuric acid to hydrogen fluoride is in the range of about 0.1: 1-1000: 1. More preferably the weight ratio is about 1: 1-100: 1, and most preferably about 2: 1-50: 1. Preferably the reaction is carried out at a temperature of about 0-100 ° C., more preferably about 0-40 ° C., and most preferably about 20-40 ° C. Extraction is usually performed at normal atmospheric pressure, but higher or lower pressure conditions may be used by those skilled in the art. When sulfuric acid is added to the mixture of fluorocarbons and HF, two phases form rapidly. A top phase rich in fluorocarbons and a bottom phase rich in HF / sulfuric acid are formed. The term "rich" means that the phase contains at least 50% of the components indicated above in the phase, preferably at least 80% of the components indicated above in the phase. The extraction efficiency of fluorocarbons by this method may range from about 90-99%.

After phase separation, the fluorocarbon rich upper phase is removed from the hydrogen fluoride and sulfuric acid rich bottom phase. This can be done by decanting, siphoning, distillation or other techniques well known in the art. The fluorocarbon extraction can be repeated by further addition of sulfuric acid on the optionally removed bottoms. Extraction efficiency of about 92% can be obtained in one step using sulfuric acid to hydrogen fluoride in a ratio of about 2.25: 1. Preferably, the hydrogen fluoride is then separated from sulfuric acid. The low solubility of HF in sulfuric acid at high temperatures may be useful for recovering HF from sulfuric acid. For example, at 140 ° C., only 4 g of HF will be dissolved in 100% sulfuric acid. HF can be recovered by heating the HF / sulfuric acid solution. HF and sulfuric acid are then recycled. That is, HF can be recycled to the previous reaction for the formation of HFC-245 and sulfuric acid can be recycled for use in further extraction steps.

In another embodiment of the invention, the recovery of the hydrogen fluoride from the mixture of fluorocarbon and hydrogen fluoride can be carried out in gas phase by a continuous process of introducing a sulfuric acid stream into the stream of fluorocarbon and hydrogen fluoride. have. This can be done in a standard scrubbing tower by flowing a stream of sulfuric acid countercurrent to a stream of fluorocarbons and hydrogen fluoride. Sulfuric acid extraction is described, for example, in US Pat. No. 5,895,639, which is incorporated herein by reference. In another embodiment, the removal of the hydrogen fluoride from the result of dehydrofluorination is carried out by passing the result through a scrubber comprising water and caustic and then drying as in a sulfuric acid drying column.

Alternatively, HF can be recovered or removed using water or caustic scrubbers or by contacting with metal salts. When using a water extractor, the technique is similar to sulfuric acid extraction. When caustic is used, HF is removed from the system only as a fluoride salt in aqueous solution. If a metal salt (eg potassium fluoride or sodium fluoride) is used, it can be used as is or in combination with water. HF can be recovered when metal salts are used. The result is a mixture comprising trans-1,3,3,3-tetrafluoropropene, cis-1,3,3,3-tetrafluoropropene and unreacted HFC-245fa.

Reactor output is about 75-90 wt% of trans-1,3,3,3-tetrafluoropropene, preferably about 75-85 wt% of trans-1,3,3,3-tetrafluoropropene, and More preferably about 75-80% by weight of trans-1,3,3,3-tetrafluoropropene.

The reactor output contains about 1-15% cis-1,3,3,3-tetrafluoropropene, preferably about 1-10% by weight cis-1,3,3,3-tetrafluoropropene. do.

The reactor output contains about 1-15% by weight of 1,1,3,3,3-pentafluoropropane, preferably about 1-10% by weight of 1,1,3,3,3-pentafluoropropane.

It is often necessary or desirable to reduce the global warming potential (GWP) of the blowing agent, aerosol or solvent composition. The reactor output implementation preferably has a GWP of about 200 or less. More preferably about 150 or less GWP. In certain circumstances, the most preferred GWP of the mixture is about 15 or less. As used herein, GWP is compared to carbon dioxide, as defined in "The Scientific Assessment of Ozone Depletion, 2002, a report of the World Meteorological Association's Gloval Ozone Research and Monitoring Project" (incorporated herein by reference). It is the effect over the 100-year time horizon. In certain preferred forms, the compositions of the present invention also preferably have an ozone depletion index of 0.05 or less, more preferably 0.02 or less, and more preferably about zero. As used herein, "ODP" is as defined in "The Scientific Assessment of Ozone Depletion, 2002, A report of the World Meteorolgical Association's Global Ozone Research and Monitoring Project" (incorporated herein by reference).

Further embodiments of the reactor composition relate to maintaining the nonflammable or low flammability of the blowing agent, aerosol propellant or solvent composition.

One or more auxiliary blowing agents, auxiliary propellants or auxiliary solvents are useful and provide efficacy in a variety of applications in terms of insulation performance, pressure performance or solubility without the deleterious effects caused by molar gas capacity, flammability reduction or GWP reduction. Such adjuvants include, but are not limited to, hydrofluorocarbons, C ₁ -C ₆ hydrocarbons, C ₁ -C ₈ alcohols, ethers, diethers, aldehydes, ketones, hydrofluoroethers, C ₁ -C ₄ chlorocarbons, At least one additional component of methyl formate, water, carbon dioxide, C ₃ -C ₄ hydrofluoroolefins, and C ₃ -C ₄ hydrochlorofluoroolefins. Examples of these components include, but are not limited to, difluoromethane, trans-1,2-dichloroethylene, difluoroethane, 1,1,1,2,2-pentafluoroethane, 1,1,2 , 2-tetrafluoroethane, 1,1,1,2-tetrafluoroethane, 1,1,1-trifluoroethane, 1,1-difluoroethane, fluoroethane, HFC-236fa Hexafluoropropane isomer, pentafluoropropane isomer including HFC-245fa, heptafluoropropane isomer including HFC-227ea, hexafluorobutane isomer and pentafluorobutane isomer including HFC-365mfc, tetra One or more of the fluoropropane isomer and the trifluoropropene isomer (HFO-1243). Specifically, HFO comprising 1,1,1,2-tetrafluoropropene (HFO-1234yf), and cis- and trans-1,2,3,3-tetrafluoropropene (HFO-1234ye) All molecules and isomers of -1234, HFC-1233zd and HFC-1225ye are included.

Preferred auxiliary blowing agents include, but are not limited to:

Hydrocarbons, methyl formate, halogen-containing compounds, in particular fluorine-containing compounds such as halocarbons, fluorocarbons, chlorocarbons, fluorochlorocarbons and chlorine-containing compounds, hydrofluorocarbons, hydrochlorocarbons, hydrofluorochlorocarbons , Halogenated hydrocarbons such as hydrofluoroolefins, hydrochlorofluoroolefins, CO ₂ , CO ₂ generating materials such as water, and organic acids that produce CO ₂ , such as formic acid. Examples include, but are not limited to, ethane, propane (s), ie normal pentane, isopropane, isopentane and cyclopentane; Butane (s), ie normal butane and isobutane; Ethers and halogenated ethers; Trans 1,2-dichloroethylene, pentafluorobutane; Pentafluoropropane; Hexafluoropropane; And heptafluoropropane; 1-chloro-1,2,2,2-tetrafluoroethane (HCFC-124); And 1,1-dichloro-1-fluoroethane (HCFC-141b) as well as 1,1,2,2-tetrafluoroethane (HFC-134); 1,1,1,2-tetrafluoroethane (HFC-134a); 1-chloro 1,1-difluoroethane (HCFC-142b); 1,1,1,3,3-pentafluorobutane (HFC-365mfc); 1,1,1,2,3,3,3-heptafluoropropane (HCF-227ea); Trichlorofluoromethane (CFC-11), dichlorodifluoromethane (CFC-12); 1,1,1,3,3,3-hexafluoropropane (HFC-236fa); 1,1,1,2,3,3-hexafluoropropane (HFC-236ea); Difluoromethane (HFC-32); Difluoroethane (HFC-152a); 1,1,1,3,3-pentafluoropropane (HFC-245fa); Trifluoropropene, pentafluoropropene, chlorotrifluoropropene, tetrafluoropropene including 1,1,1,2-tetrafluoropropene (HFO-1234yf), 1,1, Low-boiling, aliphatic hydrocarbons such as 1,2,3-pentafluoropropene (HFO-1225ye), and 1-chloro-3,3,3-trifluoropropene (HCFC-1233zd). Combinations of any of the above may be used. The relative amounts of any of the additional auxiliary blowing agents mentioned above, as well as any additional components included in the composition of the present invention, may vary widely within the broad general scope of the present invention, depending upon the particular application to the composition, and all such relative amounts may be It is considered to be within the scope of the present invention. In a preferred embodiment, the auxiliary blowing agent, auxiliary propellant or auxiliary solvent is in an amount of about 5-50% by weight, preferably about 10-40% by weight, and more preferably about 10-20% by weight of the total blowing agent, propellant or solvent composition. exist.

In one aspect of the present invention, a foam composition is provided. As known in the art, foam compositions generally comprise one or more foam formers and foaming agents capable of forming a foam.

It comprises a component or combination of components that can form a foam structure, preferably a cell foam structure in general. The foaming composition of the present invention comprises these components and the blowing agent compound according to the present invention. In certain embodiments, the at least one foamable formable component includes a foamable thermoset composition and / or a foaming composition. Examples of thermosetting compositions include polyurethane and polyisocyanurate foam compositions, and also phenol foam compositions. These include polyurethane prepolymers as in the example of one component foams. This reaction and forming process can be enhanced through the use of various additives such as catalyst and surfactant materials to control and control the cell size and to stabilize the foam structure during formation.

It is also contemplated that any one or more of the additional components mentioned above for the blowing agent compositions of the present invention may be incorporated into the foaming compositions of the present invention. In such thermoset foam embodiments, one or more compositions of the present invention are included as foaming agents or included as part of a foaming agent in the foaming composition, or preferably comprise one or more components that can be reacted and / or foamable under appropriate conditions to form a foam or cell structure. It is included as part of two or more foam compositions.

The present invention provides a polyol premix composition comprising a combination of the blowing agent of the present invention, at least one polyol, at least one catalyst and optionally at least one surfactant. The blowing agent component is generally present in the polyol premix composition in an amount of about 1-30% by weight, preferably about 3-25% by weight, and more preferably about 5-25% by weight of the polyol premix composition.

The polyol component, including the polyol mixture, may be any polyol that reacts in a known manner with isocyanates in preparing polyurethane or polyisocyanurate foams. Useful polyols include one or more sucrose containing polyols; Phenols, phenol formaldehyde-containing polyols; Glucose containing polyols; Sorbitol-containing polyols; Methylglucoside containing polyols; Aromatic polyester polyols; Polyols, glycerol derived from natural products (eg soybeans); Ethylene glycol; Diethylene glycol; Propylene glycol; Graft copolymers of polyether polyols and vinyl polymers; Copolymers of polyether polyols and polyureas; One or more (a) condensed into one or more (b): (a) glycerin, ethylene glycol, diethylene glycol, trimethylolpropane, ethylene diamine, pentaerythritol, soybean oil, lecithin, tall oil, palm oil, castor oil; (b) ethylene oxide, propylene oxide, mixtures of ethylene oxide and propylene oxide, or combinations thereof. The polyol component is usually present in the polyol premix composition in an amount of about 60-95%, preferably about 65-95%, and more preferably about 70-90% by weight of the polyol premix composition.

Polyol premixes may also include a catalyst. Useful catalysts are primary amines, secondary amines or most typical tertiary amines. Useful tertiary amine catalysts include, but are not limited to, dicyclohexylmethylamine; Ethyldiisopropylamine; Dimethylcyclohexylamine; Dimethylisopropylamine; Methylisopropylbenzylamine; Methylcyclopentylbenzylamine; Isopropyl-sec-butyl-trifluoroethylamine; Diethyl- (α-phenylethyl) amine, tri-n-propylamine, or a combination thereof. Useful secondary amine catalysts include, but are not limited to, dicyclohexylamine; t-butylisopropylamine; Di-t-butylamine; Cyclohexyl-t-butylamine; Di-sec-butylamine, dicyclopentylamine; Di- (α-trifluoromethylethyl) amine; Di- (α-phenylethyl) amine; Or combinations thereof.

Useful primary amine catalysts include, but are not limited to, triphenylmethylamine and 1,1-diethyl-n-propylamine.

Other useful amines include morpholines, imidazoles, ether containing compounds and the like. This is

Dimorpholinodiethyl ether

N-ethylmorpholine

N-methylmorpholine

Bis (dimethylaminoethyl) ether

Imidazole

n-methylimidazole

1,2-dimethylimidazole

Dimorpholinodimethyl ether

N, N, N ', N', N ", N" -pentamethyldiethylenetriamine

N, N, N ', N', N ", N" -pentaethyldiethylenetriamine

N, N, N ', N', N ", N" -pentamethyldipropylenetriamine

Bis (diethylaminoethyl) ether

Bis (dimethylaminopropyl) ether

It includes.

The amine catalyst is usually present in the polyol premix composition in an amount of about 0.2-8.0 weight percent, preferably about 0.4-7.0 weight percent, and more preferably about 0.7-6.0 weight percent of the polyol premix composition.

The polyol premix composition may optionally further comprise a non-amine catalyst. Suitable non-amine catalysts are bismuth, lead, tin, titanium, antimony, uranium, cadmium, cobalt, torium, aluminum, mercury, zinc, nickel, cerium, molybdenum, vanadium, copper, manganese, zirconium, sodium, potassium Or organometallic compounds containing combinations thereof. This includes, but is not limited to, bismuth nitrate, lead 2-ethylhexate, lead benzoate, ferric chloride, antimony trichloride, antimony glycolate, tin salts of carboxylic acids, dialkyl tin salts of carboxylic acids , Potassium acetate, potassium octoate, potassium 2-ethylhexate, glycine salts, quaternary ammonium carboxylates, alkali metal carboxylates, and N- (2-hydroxy-5-nonylphenol) methyl-N-methyl Glycinate, tin (II) 2-ethylhexanoate, dibutyltin dilaurate or combinations thereof. If any non-amine catalyst is used, it is generally polyol premix in an amount of about 0.01-2.5%, preferably about 0.05-2.25%, and more preferably about 0.10-2.00% by weight of the polyol premix composition. Present in the composition. This is a general amount, and the quantitative amount of the metal catalyst can vary widely, and an appropriate amount can be easily determined by those skilled in the art.

The polyol premix composition then contains any silicone surfactant. Silicone surfactants are used to form the foam from the mixture and also to control the foam size of the foam so that the foam of the desired cell structure is obtained. Preferably, foam having small bubbles or cells inside of uniform size is preferred. This is because these foams have the most desirable physical properties such as breakdown strength and thermal conductivity. It is also important to have a foam with a stable cell that does not collapse before or during foam formation.

The polyol premix composition may optionally contain non-silicone surfactants, such as non-silicone, non-ionic surfactants. This includes oxyethylated alkylphenols, oxyethylated fatty alcohols, paraffin oils, castor oil esters, ricinoleic acid esters, lot oils, peanut oils, paraffins and fatty alcohols. Preferred non-silicone non-ionic surfactants are LK-443, which is commercially available from Air Products Corporation. If non-silicone, non-ionic surfactants are used, they are polyol premixes in an amount of about 0.25-3.0 weight percent, preferably about 0.5-2.5 weight percent, and more preferably about 0.75-2.0 weight percent of the polyol premix composition. It is generally present in the composition.

The present invention also provides a process for preparing a polyurethane or polyisocyanurate foam comprising reacting an organic polyisocyanate with a polyol premix composition. The preparation of polyurethane or polyisocyanurate foams using the compositions described herein may be used by any method well known in the art (see Saunders and Frisch, Volumes I and II Polyurethanes Chemistry and technology, 1962, John Wiley). and Sons, New York, NY or Gum, Reese, Ulrich, Reaction Polymers, 1992, Oxford University Press, New York, NY or Klempner and Sendijarevic, Polymeric Foams and Foam Technology, 2004, Hanser Gardner Publications, Cincinnati, OH). Generally, polyurethane or polyisocyanurate foams are prepared by mixing isocyanates, the polyol premix compositions and other materials such as any flame retardants, colorants or other additives. Such foams may be rigid, flexible, or semi-rigid, and may have a closed cell structure or an open cell structure, or may consist of a mixture of open and closed cells.

It is convenient in many applications to provide the components for polyurethane or polyisocyanurate foam in a premixed formulation. Most typically, the foam blend is premixed into two components. Isocyanates and any other isocyanate compatible raw materials generally include a primary component called the "A" component. Polyol mixed compositions comprising a surfactant, a catalyst, a blowing agent and any other components generally comprise a secondary component, referred to as the "B" component. In any given application, the component "B" may not contain all of the components listed above. For example, some formulations omit flame retardants if they are not necessarily foam properties where flame resistance is necessary. Accordingly, the polyurethane or polyisocyanurate foams are easily prepared by hand mixing in small quantities, preferably by tying together the A and B components together using mechanical mixing techniques to produce blocks, slabs, laminates, injection panels and Other items, spray applied foam, pross, and the like. Optionally, other components such as nucleating agents, flame retardants, colorants, waxes, process additives, auxiliary blowing agents, water, and other polyols can be added to the mixing head or reaction section as a stream. Most conveniently, however, they are all incorporated into one B component as described above. The blowing agent may be added to the isocyanate or in a separate third stream in the A- or B-part.

Foam compositions suitable for forming polyurethane or polyisocyanurate foams can be formed by reacting the organic polyisocyanate with the polyol premix composition. Any organic polyisocyanate can be used for the synthesis of polyurethane or polyisocyanurate foams comprising aliphatic and aromatic polyisocyanates. Suitable organic polyisocyanates include aliphatic, cycloaliphatic, aromatic aliphatic, aromatic and heterocyclic isocyanates well known in the polyurethane chemistry. These are described, for example, in US Pat. No. 4,868,224; 3,401,190; 3,454,606; 3,227,138; 3,492,330; 3,001,973; 3,394,164; 3,124,605 and 3,201,372. Preferred species are aromatic polyisocyanates.

Representative organic polyisocyanates correspond to the formula:

R (NCO) z

Wherein R is a polyvalent organic radical that is aliphatic, aralkyl, aromatic or mixtures thereof, and z is an integer corresponding to the valence of R and is at least 2. Representative organic polyisocyanates expected in the present invention are, for example, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, mixtures of 2,4- and 2,6-toluene diisocyanate, crude toluene diisocyanate Aromatic diisocyanates such as methylene diphenyl diisocyanate, crude methylene diphenyl diisocyanate and the like; Aromatic triisocyanates such as 4,4 ', 4 "-triphenylmethane triisocyanate, 2,4,6-toluene triisocyanate; 4,4'-dimethyldiphenylmethane-2,2', 5,5'-tetra Aromatic tetraisocyanates such as isocyanates, etc .; arylalkyl polyisocyanates such as xylylene diisocyanates; aliphatic polyisocyanates such as hexamethylene-1,6-diisocyanate, lysine diisocyanate methylester, etc .; and mixtures thereof. Isocyanates include polymethylene polyphenylisocyanates, hydrogenated methylene diphenylisocyanates, m-phenylene diisocyanates, naphthylene-1,5-diisocyanates, 1-methoxyphenylene-2,4-diisocyanates, 4,4 '-Biphenylene diisocyanate, 3,3'-dimethoxy-4,4'-biphenyl diisocyanate, 3,3'-dimethyl-4,4'-biphenyl isocyanate , And 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate Typical aliphatic polyisocyanates include alkylene diisocyanates such as trimethylene diisocyanate, tetramethylene diisocyanate and hexamethylene diisocyanate, Isophorene diisocyanate, 4,4'-methylenebis (cyclohexyl isocyanate) and the like; typical aromatic polyisocyanates are m-, and p-phenylene diisocyanate, polymethylene polyphenyl isocyanate, 2,4- and 2,6 Toluene diisocyanate, dianisidine diisocyanate, bitoylene isocyanate, naphthylene 1,4-diisocyanate, bis (4-isocyanatophenyl) methene, bis (2-methyl-4-isocyanatophenyl) methane, etc. Preferred polyisocyanates are polymethylene polyphenyl isocyanates, in particular methylenebis (phenyl is Preference is given to mixtures containing the balance of 30-85% by weight of the mixture) and the remainder of the mixture comprising polymethylene polyphenyl polyisocyanates of at least two functional groups, such polyisocyanates being prepared by conventional methods known in the art. In the present invention, polyisocyanates and polyols are used in amounts that produce an NCO / OH stoichiometric ratio in the range of about 0.9-5.0. In the present invention, the NCO / OH equivalent ratio is preferably about 1.0 or more and about 3.0 or less, and the ideal range is about 1.1-2.5. Particularly suitable organic polyisocyanates include polymethylene polyphenyl isocyanates, methylenebis (phenyl isocyanates), toluene diisocyanates, or combinations thereof. In preparing the polyisocyanurate foams, trimmerization catalysts are used for the purpose of converting the blends mixed with the excess A component into polyisocyanurate-polyurethane foams. The trimmerization catalyst used can be any catalyst known to those skilled in the art, including but not limited to glycine salts, tertiary amine trimerization catalysts, quaternary ammonium carboxylates, and alkali metal carboxylates and these various types of A mixture of catalysts. Preferred species in this class are potassium acetate, potassium octoate, and N- (2-hydroxy-5-nonylphenol) methyl-N-methylglycinate.

Conventional flame retardants may also be incorporated, preferably in amounts of up to 20% by weight of the reactants. Optional flame retardants include tris (2-chloroethyl) phosphate, tris (2-chloropropyl) phosphate, tris (2,3-dibromopropyl) phosphate, tris (1,3-dichloropropyl) phosphate, tri (2 -Chloroisopropyl) phosphate, tricresyl phosphate, tri (2,2-dichloroisopropyl) phosphate, diethyl N, N-bis (2-hydroxyethyl) aminomethylphosphonate, dimethyl methylphosphonate, Tri (2,3-dibromopropyl) phosphate, tri (1,3-dichloropropyl) phosphate, and tetra-kiss- (2-chloroethyl) ethylene diphosphate, triethylphosphate, diammonium phosphate, various halogenated aromatics Compounds, antimony oxides, aluminum trihydrate, polyvinyl chloride, melamine and the like. Other optional ingredients include 0 to about 7% of water, which chemically reacts with isocyanates to produce carbon dioxide. Carbon dioxide acts as an auxiliary blowing agent. Formic acid is also used to react with isocyanates to produce carbon dioxide, optionally added to the "B" component.

In addition to the aforementioned components, other components such as dyes, fillers, pigments and the like may be included in the preparation of the foam. Dispersants and cell stabilizers can be incorporated into the blends of the present invention. Conventional fillers used in the present invention include, for example, aluminum silicate, calcium silicate, magnesium silicate, calcium carbonate, barium sulfate, calcium sulfate, glass fibers, carbon black and silica. When fillers are used, they are generally present in a weight in the range of about 5-100 parts per 100 parts of polyol. Pigments that can be used in the present invention include titanium dioxide, zinc oxide, iron oxide, antimony oxide, chrome green, chrome yellow, iron blue sienas, molybdate orange and para red, benzidine yellow, toluidine red, toner and phthalocyanine; It may be any conventional pigment, such as the same organic pigment.

The resulting polyurethane or polyisocyanurate foam has a density of about 0.5 pounds per cubic foot to about 60 pounds per cubic foot, preferably about 1.0-20.0 pounds per cubic foot, and most preferably about 1.5-6.0 pounds per cubic foot Can vary. The density obtained correlates with how much the amount of blowing agent or blowing agent mixture disclosed herein and in addition auxiliary blowing agents such as water or other auxiliary blowing agents are present in the A and / or B components or alternatively added during foam preparation. Is in. Such foams may be rigid, flexible, or semi-rigid, and may have a closed cell structure or an open cell structure, or may consist of a mixture of open and closed cells. Such foams are used in a variety of well known applications including, but not limited to, thermal insulation, cushioning, flotation, packaging, adhesives, void filling, kraft and decoration, and shock absorption.

In certain other embodiments of the present invention, the at least one foamable component comprises a thermoplastic material, in particular a thermoplastic polymer and / or resin. Examples of thermoplastic foams include polyolefins such as monovinyl aromatic compounds of the formula Ar-CHCH ₂ , where Ar is an aromatic hydrocarbon radical of the benzene series such as polystyrene (PS). Other examples of suitable polyolefin resins according to the present invention include various ethylene-based polymers, including polyethylene and ethylene homopolymers such as ethylene copolymers, polypropylene-based polymers and polyethylene terephthalate polymers. In certain embodiments, the thermoplastic foam composition is an extrudable composition.

It will be generally appreciated by those skilled in the art, in particular in light of the present specification, that the order and method by which the blowing agents of the present invention are added to the foaming composition generally does not affect the performance of any application of the present invention.

The present invention will be described in detail through the following examples.

Example 1

Fluorinated Cr ₂ O ₃ HFC-245fa dehydrofluorination via

The catalyst used in this example was 20 cc of fluorinated chromia catalyst (Cr ₂ O ₃ fluorinated). A HFC-245fa feed of at least 99% purity was passed through the catalyst at a rate of 12 g / h at a temperature in the range of 250-350 ° C. As shown in Table 1, as the reaction temperature was increased from 250 ° C. to 350 ° C., the HFC-245fa conversion increased from 65.2% to 96.0% and the selectivity for trans-1234ze was slightly from 84.7% to 80.6%. Decreased. At 250 ° C., trans / cis-1234ze was shown to be just a product. At 350 ° C., after about 8 hours of activation, the conversion and selectivity of HFC-245fa to 1234ze remained at the same level during this test period lasting 72 hours. These results show that the fluorinated Cr ₂ O ₃ catalyst is very active and selective for converting HFC-245fa to cis-1234ze and trans-1234ze, and the catalyst has very high stability.

Effect of Reaction Temperature on the Performance of “Fluorinated Chromia Catalyst” During HFC-245fa Dehydrofluorination Temperature (℃) HFC-245fa conversion rate% Trans-1234ze selectivity% Cis-1234ze selectivity% Unknown selectivity% Trans-1234ze lbs / hr / ft ³ 350 96.0 80.6 18.0 1.4 26.0 300 90.2 83.0 16.8 0.2 25.1 275 81.5 83.9 16.0 0.1 23.0 250 65.2 84.7 15.3 0.0 18.5

Reaction conditions: 20 cc catalyst, 12 g / h HFC-245fa, 1 atm.

Example 2

HFC-245fa dehydrofluorination via metal fluoride catalyst

The catalyst used in this example comprises three metal fluoride catalysts, AlF ₃ , FeF ₃ and 10% MgF ₂ -90% AlF ₃ . 20 cc of each catalyst was used during the reaction. A HFC-245fa feed of greater than 99% purity was passed through these three catalysts at 350 ° C. at a rate of 12 g / h. As shown in Table 2, both AlF ₃ and 10% MgF ₂ -90% AlF _{3 provided} high activity (> 95% HFC-245fa conversion) for HFC-245 dehydrofluorination, while FeF ₃ was significantly more Low activity (<60% HFC-245fa conversion). The selectivity for HFO-trans-1234ze through AlF ₃ and 10% MgF ₂ -90% AlF ₃ catalyst was about 80% at 350 ° C.

HFC-245fa dehydrofluoride via metal fluoride catalyst catalyst HFC-245fa conversion rate% Trans-1234ze selectivity% Cis-1234ze selectivity% Unknown selectivity% Trans-1234ze lbs / hr / ft ³ AlF ₃ 96.8 80.4 16.3 3.3 26.2 FeF ₃ 55.4 78.3 21.1 0.6 14.6 10% MgF ₂ -90% AlF ₃ 98.3 78.6 17.5 4.0 26.0

Reaction conditions: 20 cc catalyst, 12 g / h HFC-245fa, 350 ° C., 1 atm.

Example 3

HFC-245fa dehydrofluorination via activated carbon supported metal catalyst

The catalyst used in this example comprises three activated carbon supported metal catalysts, 0.5 wt% Fe / AC, 0.5 wt% Ni / AC and 5.0 wt% Co / AC. 20 cc of each catalyst was used during the reaction. A HFC-245fa feed of greater than 99% purity was passed through each of these three catalysts at 350 ° C. at a rate of 12 g / h. As shown in Table 3, iron showed the highest activity among the activated carbon supported non-noble metal catalysts.

0.5 wt% Fe / AC catalyst at a reaction temperature of 525 ° C. provided about 91% cis / trans-1234ze selectivity and about 80% HFC-245fa conversion.

HFC-245fa dehydrofluorination via activated carbon supported metal catalyst at 525 ° C catalyst HFC-245fa conversion rate% Trans-1234ze selectivity% Cis-1234ze selectivity% Unknown selectivity% Trans-1234ze lbs / hr / ft ³ 0.5 wt% Fe / AC 80.0 67.8 23.4 8.8 18.2 0.5 wt% Ni / AC 24.8 46.6 16.6 36.8 3.9 5.0 wt% Co / AC 10.9 20.1 7.2 72.7 0.7

Reaction conditions: 20 cc catalyst, 12 g / h HFC-245fa, 525 ° C., 1 atm

Example 4

HFC-245fa is added to a reactor containing 20 wt% KOH solution at 70 ° C. and the pressure is monitored. The molar ratio of KOH to HFC-245fa is maintained at 1.5-10.0. This caustic extracts HF against HFC-245fa and forms KF. Simultaneous increase in pressure indicates that low boiling point HFO-1234ze isomers are being formed. The reaction is essentially complete within 24 hours. Volatile gases are collected and analyzed by gas chromatography, which together with some unreacted HFC-245fa are found to consist of the trans- and cis-isomers of HFO-1234ze in about a 4: 1 ratio.

Example 5 (foaming test)

The polyol (component B) blend contains 100 parts by weight of a polyol blend, 1.5 parts by weight of Niax L6900 silicone surfactant, 1.5 parts by weight of water, N, N, N ', N', N ", N" -pentamethyldiethylenetriamine ( Sold as Polycat 5 by Air Products and Chemicals) 1.2 parts by weight, 2.4 parts by weight of isocaproic acid, and trans-1,3,3,3-tetrafluoropropene, cis-1,3,3,3- 8 parts by weight of a blowing agent comprising tetrafluoropropene and 1,1,1,3,3-pentafluoropropane. When freshly prepared and mixed with 120.0 parts of Lupranate M20S polymeric isocyanate, the total B component composition produces a good quality foam with a fine and regular cell structure. Foam reactivity is typical for pour in place foaming with a gel time of 105 seconds. The total B-side composition (114.6 parts) is aged at 120 ° F. for 62 hours and then mixed with 120.0 parts M 2 OS Iso polyisocyanate to form a foam. The foam has a general appearance without cell collapse. Gel time is 150 seconds.

Example 6

70% by weight of trans-1,3,3,3-tetrafluoropropene, 5% by weight of cis-1,3,3,3-tetrafluoropropene, 1,1,1,3,3-pentafluoro 10% by weight of ropropane and hydrofluorocarbons, C ₁ -C ₆ hydrocarbons, C ₁ -C ₈ alcohols, ethers, diethers, aldehydes, ketones, hydrofluoroethers, C ₁ -C ₄ chlorocarbons, methyl foam A blowing agent comprising 15% by weight of one or more components of mate, carbon dioxide, C ₃ -C ₄ hydrofluoroolefins and C ₃ -C ₄ hydrochlorofluoroolefins is prepared. The blowing agents are individually mixed with polystyrene, polyethylene, polypropylene or polyethylene terephthalate to produce a high quality thermoplastic foam having a fine and regular cell structure.

Example 7

75% by weight of trans-1,3,3,3-tetrafluoropropene, 7% by weight of cis-1,3,3,3-tetrafluoropropene, 1,1,1,3,3-pentafluoro 13% by weight of ropropanol and hydrofluorocarbons, C ₁ -C ₆ hydrocarbons, C ₁ -C ₈ alcohols, ethers, diethers, aldehydes, ketones, hydrofluoroethers, C ₁ -C ₄ chlorocarbons, methyl foam A blowing agent comprising 5% by weight of one or more components of mate, water, carbon dioxide, C ₃ -C ₄ hydrofluoroolefin and C ₃ -C ₄ hydrochlorofluoroolefin is prepared. The blowing agents are mixed with polyurethane or polyisocyanurate individually, resulting in a high quality thermoplastic foam having a fine and regular cell structure.

Example 8- Polystyrene Foam

This example shows a blowing agent for polystyrene foam formed in a twin screw type extruder. The apparatus used in this example is a Leistritz twin screw extruder having the following characteristics:

30mm co-rotating screw

L: D ratio = 40: 1

90 wt% trans-1,3,3,3-tetrafluoropropene, 5 wt% cis-1,3,3,3-tetrafluoropropene and 1,1,1,3,3-pentafluoro A foaming agent comprising 5% by weight of ropropan is prepared. The extruder is divided into 10 sections, each representing a 4: 1 L: D. The polystyrene resin is introduced into the first section, the blowing agent is introduced into the sixth section, and the extrudate is discharged into the tenth section. The extruder basically operates as a melt / mixed extruder. Subsequent chilled extruders are connected side by side, the design characteristics of which are as follows:

Leistritz Twin Screw Extruder

40mm co-rotating screw

L: D ratio = 40: 1

Die: 5.0mm round

Polystyrene resin, ie Nova Chemical (a generic extrusion grade polystyrene called Nova 1600), is fed to the extruder under these conditions. The resin has a melting temperature of 375-525 ° F. The pressure of the extruder at the die is about 1320 pounds per square inch (psi) and the temperature at the die is about 115 ° C. A blowing agent is added to the extruder at this location and about 0.5% by weight of talc is added as nucleating agent based on the weight of the total blowing agent. Foams are prepared using the blowing agents at concentrations of 10%, 12% and 14% by weight. The density of the foam produced is in the range of about 0.1-0.07 grams per cubic centimeter and has a cell size of about 49-68 microns. The foam, about 30 millimeters in diameter, is visually of very good quality, very fine cell size, with no or no pores or voids.

Example 9-Polyurethane Foam

Example 8 is repeated except using a composition capable of forming a polyurethane foam, producing a good quality polyurethane foam with a fine and regular cell structure.

Example 10-Polyisocyanurate Foam

Example 8 is repeated except using a composition capable of forming a polyisocyanurate foam, producing a good quality polyisocyanurate foam with a fine and regular cell structure.

Example 11-Phenolic Foam

Example 8 is repeated except using a composition capable of forming a phenolic foam, producing a good quality phenolic foam with a fine and regular cell structure.

Example 12-Thermoplastic Foam

Example 8 is repeated except that a composition capable of forming a thermoplastic foam is used. The following components are each used: monovinyl aromatic compounds, ethylene-based compounds, propylene-based polymers, polystyrenes, ethylene homopolymers, polypropylenes, and polyethylene terephthalates. Excellent quality thermoplastic polyolefin foams with fine and regular cell structures are produced.

While the invention has been shown and described in detail with reference to preferred embodiments, it will be readily appreciated by those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention. It is intended that the claims cover the disclosed embodiments, the above mentioned alternatives and all equivalents thereof.

Claims (20)

About 75-90% by weight of trans-1,3,3,3-tetrafluoropropene, about 1-15% by weight of cis-1,3,3,3-tetrafluoropropene and 1,1,3, 3,3-pentafluoropropane blowing agent comprising about 1-15% by weight.
The blowing agent of claim 1 comprising about 75-85% by weight of trans-1,3,3,3-tetrafluoropropene.
The blowing agent of claim 1 comprising about 1-10% by weight of cis-1,3,3,3-tetrafluoropropene.
The method of claim 1, wherein about 75-85 weight percent of trans-1,3,3,3-tetrafluoropropene, about 1-10 weight percent of cis-1,3,3,3-tetrafluoropropene and A blowing agent comprising about 1-10% by weight of 1,1,3,3,3-pentafluoropropane.
The blowing agent of claim 1 having a global warming index of about 200 or less.
i) about 50-95% by weight of the blowing agent of claim 1; And
ii) hydrofluorocarbons, C ₁ -C ₆ hydrocarbons, C ₁ -C ₈ alcohols, ethers, diethers, aldehydes, ketones, hydrofluoroethers, C ₁ -C ₄ chlorocarbons, methyl formate, water, About 5-50% by weight auxiliary blowing agent comprising at least one component of carbon dioxide, C ₃ -C ₄ hydrofluoroolefins and C ₃ -C ₄ hydrochlorofluoroolefins
Foaming agent composition comprising a.
The method of claim 6, wherein the one or more components are difluoromethane, trans-1,2-dichloroethylene, difluoroethane, 1,1,1,2,2-pentafluoroethane, 1,1,2 , 2-tetrafluoroethane, 1,1,1,2-tetrafluoroethane, 1,1,1-trifluoroethane, 1,1-difluoroethane, fluoroethane, hexafluoropropane, Pentafluoropropane, heptafluoropropane, hexafluorobutane, pentafluorobutane, tetrafluoropropane, trifluoropropene, tetrafluoropropene and pentafluoropropene Foaming agent composition.
A foaming composition comprising the blowing agent of claim 1 and a foam forming component or a mixture of components capable of forming a foam structure.
10. The foaming composition of claim 8 wherein the foam forming component or mixture of components capable of forming a foam structure comprises at least one thermosetting component.
10. The foaming composition of claim 9 wherein the at least one thermosetting component comprises a composition capable of forming a polyurethane foam.
10. The foaming composition of claim 9 wherein the at least one thermosetting component comprises a composition capable of forming a polyisocyanurate foam.
10. The foaming composition of claim 9 wherein said at least one thermosetting component comprises a composition capable of forming a phenolic foam.
10. The foaming composition of claim 8 wherein the foam forming component, or a mixture of components capable of forming a foam structure, comprises at least one thermoplastic component.
14. The foaming composition of claim 13 wherein said at least one thermoplastic component comprises a polyolefin.
15. The foaming composition of claim 14 wherein the polyolefin comprises at least one of a monovinyl aromatic compound, an ethylene compound and a propylene polymer.
The foaming composition of claim 15 wherein the polyolefin comprises at least one of polystyrene, ethylene homopolymer, polypropylene, and polyethylene terephthalate.
a) about 75-90 wt% of trans-1,3,3,3-tetrafluoropropene, about 1-15 wt% of cis-1,3,3,3-tetrafluoropropene, and 1,1 Blowing agent comprising about 1-15% by weight of 3,3,3-pentafluoropropane; And
b) a foam forming component or a mixture of components capable of forming a foam structure
Foam forming method comprising the step of mixing.
18. The method of claim 17, wherein the blowing agent is about 75-90 weight percent trans-1,3,3,3-tetrafluoropropene, about 1-10 weight cis-1,3,3,3-tetrafluoropropene % And about 1-10% by weight of 1,1,3,3,3-pentafluoropropane.
a) i) about 75-90 weight percent of trans-1,3,3,3-tetrafluoropropene, about 1-15 weight percent of cis-1,3,3,3-tetrafluoropropene, and 1 About 50-95 weight percent of a blowing agent comprising about 1-15 weight percent of 1,3,3,3-pentafluoropropane; And
ii) hydrofluorocarbons, C ₁ -C ₆ hydrocarbons, C ₁ -C ₈ alcohols, ethers, diethers, aldehydes, ketones, hydrofluoroethers, C ₁ -C ₄ chlorocarbons, methyl formate, water, About 5-50% by weight of an auxiliary blowing agent comprising at least one component of carbon dioxide, C ₃ -C ₄ hydrofluoroolefin and C ₃ -C ₄ hydrochlorofluoroolefin; And
b) a foam forming component or a mixture of components capable of forming a foam structure
Foam forming method comprising the step of mixing.
20. The method of claim 19, wherein the blowing agent is about 75-90 weight percent of trans-1,3,3,3-tetrafluoropropene, and about 1-10 cis-1,3,3,3-tetrafluoropropene. Weight percent, and about 1-10 weight percent 1,1,3,3,3-pentafluoropropane.